The electrochemistry of deoxyribonucleic acid is booming due to the expectations of the development of electrochemical transducer-based devices for its damage and detection of nucleotide sequences. In this article, the recent developments of the interaction between DNA and electrode, the electrochemical reaction of DNA, the electrochemical studies of the interaction between transition metal complexes are first introduced, with emphasis being placed on the review of the current state of research on the applications of transition metal complexes in long-distance electron transfer through DNA helix, DNA electrochemical sensors, electrogenerated chemiluminescence labeling analysis and damage repair of DNA. With these described above as basis, some related suggestions are given.